CN113258084A - Doped transition metal monoatomic catalyst, preparation method and application - Google Patents
Doped transition metal monoatomic catalyst, preparation method and application Download PDFInfo
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- CN113258084A CN113258084A CN202110405125.2A CN202110405125A CN113258084A CN 113258084 A CN113258084 A CN 113258084A CN 202110405125 A CN202110405125 A CN 202110405125A CN 113258084 A CN113258084 A CN 113258084A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The application relates to the technical field of catalysts, and provides a preparation method of a doped transition metal monatomic catalyst, which comprises the following steps: dissolving soluble transition metal salt solution, sp2Fully mixing the carbon material and the nitrogen-containing compound, and recovering and drying to obtain a solid compound; dispersing the solid compound in a solvent to obtain a mixed solution; providing an inert atmosphere, mixing the mixed solution with a reducing agent to perform a reduction reaction, and drying to obtain a monatomic catalyst precursor; and calcining the monatomic catalyst precursor to obtain the doped transition metal monatomic catalyst. The preparation method is simple, washing is not needed, the cost is low, and the prepared doped transition metal monatomic catalyst is good in dispersity, high in stability and excellent in catalytic activity, and is resistant to agglomeration and suitable for wide application.
Description
Technical Field
The application belongs to the technical field of catalysts, and particularly relates to a doped transition metal monatomic catalyst, and a preparation method and application thereof.
Background
In the technical field of catalysis, catalysts with high development utilization rate, good effect and low price are hot spots of research, and monatomic catalysts are used as bridges of homogeneous catalysis and heterogeneous catalysts and have high efficiency of homogeneous catalysis and recoverability of heterogeneous catalysis, so that the catalysts become hot spots of research in recent years. The single atom catalyst is reported for the first time by academicians, etc. and the preparation method has accumulated a certain amount after continuous exploration. The preparation method of the prior monatomic mainly comprises the following steps: coprecipitation, impregnation, atomic layer deposition, pyrolysis, organic ligand strategies, and the like. However, the preparation process is complicated due to the angle of the preparation process and the stability of the catalyst, and the stability and the catalytic activity of the obtained monatomic catalyst are low, so that the wide application of the monatomic catalyst is limited.
Disclosure of Invention
The application aims to provide a doped transition metal monatomic catalyst, a preparation method and application thereof, and aims to solve the problems that in the prior art, the monatomic catalyst is complex in preparation process, and the obtained catalyst is low in catalytic activity and stability.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a doped transition metal monatomic catalyst, comprising the steps of:
dissolving soluble transition metal salt solution, sp2Fully mixing the carbon material and the nitrogen-containing compound, and recovering and drying to obtain a solid compound;
dispersing the solid compound in a solvent to obtain a mixed solution;
providing an inert atmosphere, mixing the mixed solution with a reducing agent to perform a reduction reaction, and drying to obtain a monatomic catalyst precursor;
and calcining the monatomic catalyst precursor to obtain the doped transition metal monatomic catalyst.
In a second aspect, the present application provides a doped transition metal monatomic catalyst, which is prepared by the preparation method of the doped transition metal monatomic catalyst.
In a third aspect, the present application provides a doped transition metal monatomic catalyst prepared by the preparation method of the doped transition metal monatomic catalyst, and an application of the doped transition metal monatomic catalyst in a battery.
In a first aspect of the present application, there is provided a process for the preparation of a doped transition metal monatomic catalyst, wherein a soluble transition metal salt solution, sp, is used2Carbon material and nitrogen-containing compound are used as raw materials, mixed reaction is carried out, and reduction and calcination treatment are carried out, wherein sp is used as raw material2Carbon material as carrier, transition metal salt as metal source, and nitrogen-containing compound with conjugated structure for contacting with each other to form sp2The pi bond in the carbon material is in a half-filled state, can interact with the nitrogen-containing compound to stabilize the nitrogen-containing compound on the surface, and simultaneously, the nitrogen-containing compound coordinates transition metal atoms through N atoms, wherein a conjugated structure acts on sp2Uniformly spreading on sp carbon material2A surface of a carbon material; uniformly doping N atoms into sp by sintering decomposition2The carbon material is divided into two parts, and metal single atoms are anchored through coordination; the preparation method is simple, washing is not needed, the cost is low, the repeatability is good, the prepared doped transition metal monatomic catalyst is good in dispersity, resistant to agglomeration, high in stability and excellent in catalytic activity, and is suitable for wide application.
The doped transition metal monatomic catalyst provided by the second aspect of the application is prepared by the preparation method of the doped transition metal monatomic catalyst, and the obtained doped transition metal monatomic catalyst is good in dispersibility, high in stability and excellent in catalytic activity, and is resistant to agglomeration, and suitable for wide application.
In the third aspect of the present application, the doped transition metal monatomic catalyst has the characteristics of good dispersibility, high agglomeration resistance, high stability and excellent catalytic activity, so that the doped transition metal monatomic catalyst can be widely applied to the field of batteries, and the catalytic reaction efficiency can be improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a scanning transmission electron microscope image of spherical aberration corrected high-angle annular dark field of graphene-supported Zn monatomic catalyst obtained in example 1 of the present application.
Fig. 2 is a transmission electron microscope image of spherical aberration corrected high-angle annular dark field scanning of the carbon nanotube-supported ruthenium monatomic catalyst obtained in example 2 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In a first aspect, embodiments of the present application provide a method for preparing a doped transition metal monatomic catalyst, comprising the steps of:
s01, dissolving soluble transition metal salt solution and sp2Fully mixing the carbon material and the nitrogen-containing compound, and recovering and drying to obtain a solid compound;
s02, dispersing the solid compound in a solvent to obtain a mixed solution;
and S03, providing a protective atmosphere, mixing the mixed solution with a reducing agent to perform a reduction reaction, drying to obtain a monatomic catalyst precursor, and calcining the monatomic catalyst precursor to obtain the doped transition metal monatomic catalyst.
In a first aspect of the present application, there is provided a process for the preparation of a doped transition metal monatomic catalyst, wherein a soluble transition metal salt solution, sp, is used2Carbon material and nitrogen-containing compound are used as raw materials, mixed reaction is carried out, and reduction and calcination treatment are carried out, wherein sp is used as raw material2Carbon material as carrier, transition metal salt as metal source, and nitrogen-containing compound with conjugated structure for contacting with each other to form sp2The pi bond in the carbon material is in a half-filled state, can interact with the nitrogen-containing compound to stabilize the nitrogen-containing compound on the surface, and simultaneously, the nitrogen-containing compound coordinates transition metal atoms through N atoms, wherein a conjugated structure acts on sp2Uniformly spreading on sp carbon material2A surface of a carbon material; uniformly doping N atoms into sp by sintering decomposition2The carbon material is divided into two parts, and metal single atoms are anchored through coordination; the preparation method is simple, washing is not needed, the cost is low, the repeatability is good, the prepared doped transition metal monatomic catalyst is good in dispersity, resistant to agglomeration, high in stability and excellent in catalytic activity, and is suitable for wide application.
In step S01, a soluble transition metal salt solution, sp2And (3) fully mixing the carbon material and the nitrogen-containing compound, and recovering and drying to obtain the solid compound.
During the reaction, soluble transition metal salt solution, sp2Carbon material and nitrogen-containing compound as raw materials, wherein sp is used for reaction2The carbon material is used as a carrier, the transition metal salt is used as a metal source, and the carbon material, the transition metal salt and the metal source are mutually contacted for subsequent use through the bridge connection effect of the nitrogen-containing compound with a conjugated structure.
Further, a soluble transition metal salt solution is provided, which is selected from soluble transition metal salt solutions, so that the transition metal salt can be completely dissolved in the solvent and completely reacted with other reactants in the reaction process.
In some embodiments, the soluble transition metal salt in the soluble transition metal salt solution is selected from at least one of a soluble sulfate, a soluble sulfite, a soluble nitrate, a soluble acetate, a soluble chloride, a soluble bromide, a soluble iodide, a soluble acetylacetonate of a transition metal. Various soluble salt solutions were chosen to ensure complete reaction with the other reactants.
Wherein the transition metal is selected from any one of Ru, Rh, Pd, Ir, Pt, Au, Fe, Co, Ni, Mn, Cu, V, Ti and Zn. Wherein, the selected transition metal salt solution needs to be soluble salt, so as to ensure that the transition metal salt solution can be well dissolved in the solvent.
In some embodiments, the soluble transition metal salt solution is: and mixing and dissolving the transition metal salt and the solvent to obtain a soluble transition metal salt solution.
Wherein the solvent is selected from at least one of water, ethanol, ethyl acetate, dichloromethane, tetrahydrofuran, toluene and pyridine, and different solvents can be selected for dissolving according to the dissolving characteristics of the provided transition metal salt. Furthermore, the dissolving temperature is 20-25 ℃ at room temperature, and the dissolving time is 10 minutes-10 hours, so that the complete dissolving is ensured.
Further, providing sp2Carbon material, sp provided2The carbon atom in the carbon material has 4 valence electrons, 3 of which generate sp2The other non-bonded electron forms a pi bond with an adjacent atom in a vertical direction, the newly formed pi bond is in a half-filled state, and the formed pi bond in the half-filled state is capable of interacting with the nitrogen-containing compound.
In some embodiments, sp2The carbon material is selected from at least one of graphene and graphene derivatives, wherein the graphene derivatives are selected from at least one of carbon nanotubes and fullerenes. All the selected graphene derivatives are sp2Carbon material having 4 valence electrons in carbon atom, 3 of which are sp generated2The other non-bonded electron forms a pi bond with the adjacent atom in the vertical direction, and the newly formed pi bond is halfIn the filled state, the resulting pi bonds in the semi-filled state are capable of interacting with the nitrogen-containing compound.
Further, nitrogen-containing compounds and sp are provided2Carbon material reacts and can be stably bonded in sp2The surface of the carbon material. In some embodiments, the nitrogen-containing compound is selected from nitrogen-containing compounds having a conjugated structure, wherein the nitrogen-containing compound having a conjugated structure has a N atom available for coordinating a metal atom, and also has a conjugated structure available for coordinating sp2The carbon material interacts. Further, in such a conjugated system in which single bonds and double bonds alternate with each other (and other types) nitrogen-containing compounds having a conjugated structure can interact with sp due to special interactions between atoms in the molecule2Strong interaction is generated by pi bonds on the surface of the carbon material, so that the strong interaction is uniformly distributed in sp2A carbon material surface; meanwhile, the nitrogen-containing compound coordinates a transition metal atom through an N atom, wherein a conjugated structure acts on sp2Uniformly spreading on sp carbon material2The surface of the carbon material.
In some embodiments, the nitrogen-containing compound having a conjugated structure is selected from at least one of substituted or unsubstituted aniline, pyridine, melamine, imidazole; all the provided nitrogen-containing compounds are nitrogen-containing compounds with conjugated structures, and experiments using the nitrogen-containing compounds can be performed with sp2Strong interaction is generated by pi bonds on the surface of the carbon material, so that the strong interaction is uniformly distributed in sp2On the other hand, the carbon material surface can coordinate transition metal atoms through N atoms, so that the transition metal atoms are uniformly spread on sp2The surface of the carbon material.
Further, a soluble transition metal salt solution, sp2In the step of sufficiently mixing the carbon material and the nitrogen-containing compound, a transition metal salt solution, sp2The carbon material and the nitrogen-containing compound are mixed in an amount of (0.01 to 4) mmol: 1 g: (0.01-4) mmol of the above-mentioned components. Based on the reaction mechanism, through determining the solution of transition metal salt, sp2The mass ratio of the carbon material to the nitrogen-containing compound can ensure that the nitrogen-containing compound coordinates with the transition metal atom through the N atomWherein the conjugated structure acts in sp2Uniformly spreading on sp carbon material2The surface of the carbon material. The washing can be avoided by accurately controlling the addition amount of the raw materials; the preparation method is simple, the operation is convenient, and if the addition amount of the transition metal salt and the nitrogen-containing compound is too large, the transition metal salt and the nitrogen-containing compound are easy to agglomerate into nano particles and cannot form a monatomic catalyst.
Further, the solid compound is obtained by recovery and drying treatment. In some embodiments, the step of recovering comprises performing centrifugation and suction filtration; wherein the centrifugal treatment is carried out for 2-10 minutes at the rotating speed of 7000-15000 r/min to obtain a precipitate; and after centrifugal treatment, carrying out suction filtration treatment, and removing water in the precipitate by adopting suction filtration treatment, so that subsequent drying treatment is facilitated.
In some embodiments, the drying process is performed to obtain a solid composite; in the drying treatment step, the temperature of the drying treatment is 60-120 ℃, the time of the drying treatment is 2-10 hours, the drying treatment is carried out, and redundant solvent is removed to obtain the solid compound.
In step S02, the solid composite is dispersed in a solvent to obtain a mixed solution.
In some embodiments, the solvent is selected from at least one of water, ethanol, ethyl acetate, dichloromethane, tetrahydrofuran, toluene, pyridine. Wherein the adding mass ratio of the solid compound to the solvent is 1: (10-30).
In step S03, a protective atmosphere is provided, the mixed solution is mixed with a reducing agent to perform a reduction reaction, and then dried to obtain a monatomic catalyst precursor, and the monatomic catalyst precursor is calcined to obtain a doped transition metal monatomic catalyst.
In some embodiments, the protective atmosphere is selected from at least one of an argon atmosphere, a nitrogen atmosphere and a hydrogen atmosphere, so that the reaction is simple and no other impurities are generated in the process of carrying out the reduction reaction and the calcination treatment, and the obtained catalyst has high purity and no other impurities.
In some embodiments, the mixed solution is mixed with a reducing agent to perform a reduction reaction, and the reduction reaction is performed by reducing transition metal ions in the mixed solution to metal monoatomic atoms by the reducing agent.
Wherein the reducing agent is at least one selected from citric acid, sodium borohydride, formaldehyde, ethylene glycol, hydrogen and carbon monoxide. According to different reducing agents, different reaction conditions are selected, and any one of heating, microwave and ultrasound is adopted. Further, the amount of the reducing agent is determined by the transition metal salt added in step S01, and the molar ratio of the reducing agent to the transition metal salt is (1-10): 1, if the addition amount of the reducing agent is too large, the reducing agent is wasted; if the amount of the reducing agent added is too small, the reduction may not be sufficient.
In some embodiments, in the step of the reduction reaction, the temperature of the reduction reaction is 25 to 500 ℃, the time of the reduction reaction is 10 minutes to 10 hours, an appropriate temperature is selected according to temperature conditions adapted to different reducing agents, and the time of the reaction is controlled.
In some embodiments, the reduction reaction is followed by a drying treatment, wherein in the drying treatment step, the temperature of the drying treatment is 60 to 120 ℃, and the time of the drying treatment is 2 to 10 hours, so as to obtain the monatomic catalyst precursor.
And further, calcining the monatomic catalyst precursor to obtain the doped transition metal monatomic catalyst. Decomposing the nitrogen-containing organic matter by calcining to uniformly dope the N atoms of the nitrogen-containing compound into sp2The carbon material is neutralized and anchors the metal monoatomic atom by coordination.
In some embodiments, in the step of calcining, the temperature of calcining is 350-1000 ℃, and the time of calcining is 10 minutes-10 hours.
In the preparation method, through sp2The interaction between the carbon material and the nitrogen-containing compound with the conjugated structure realizes the uniform distribution of the nitrogen-containing compound in sp2The carbon material surface avoids agglomeration or falling off. By precise control of sp2The carbon material, the nitrogen-containing compound having a conjugated structure, and the transition metal salt are simply mixed in a molar ratioThe preparation method has the advantages of no need of washing in the whole process, simple preparation method, simple operation steps and easy popularization. By sintering, N atoms are doped into sp2In the carbon material, the lone pair electrons in N anchor metal atoms, and the prepared single atom catalyst has high activity and high stability.
In a second aspect, the present disclosure provides a doped transition metal monatomic catalyst, which is prepared by a method for preparing a doped transition metal monatomic catalyst.
The doped transition metal monatomic catalyst provided by the second aspect of the application is prepared by the preparation method of the doped transition metal monatomic catalyst, and the obtained doped transition metal monatomic catalyst is good in dispersibility, high in stability and excellent in catalytic activity, and is resistant to agglomeration, and suitable for wide application.
In a third aspect of the embodiments of the present application, there is provided a doped transition metal monatomic catalyst prepared by the method for preparing a doped transition metal monatomic catalyst, and its use in a battery.
In the third aspect of the present application, the doped transition metal monatomic catalyst has the characteristics of good dispersibility, high agglomeration resistance, high stability and excellent catalytic activity, so that the doped transition metal monatomic catalyst can be widely applied to the field of batteries, and the catalytic reaction efficiency can be improved.
The following description will be given with reference to specific examples.
Example 1
Preparation method of graphene-loaded Zn monatomic catalyst
(1) 0.5mmol of zinc sulfate is added into 50ml of water for dissolving, 1mmol of imidazole is added as a nitrogen-containing compound after complete dissolution, and finally 1g of graphene is added, and the mixture is magnetically stirred for 5 hours.
(2) Recovering with filter paper, and drying at 60 deg.C overnight to obtain black solid.
(3) The resulting solid was redispersed in water under a nitrogen atmosphere, 0.5g sodium citrate was added as a reducing agent and stirred at 80 ℃ for 10h.
(4) Recovering with filter paper, and drying at 60 deg.C overnight to obtain black powder.
(5) And (3) putting the dried black powder into a tubular furnace, heating to 650 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, maintaining for 2 hours, and naturally cooling to room temperature to obtain black solid powder, namely the graphene-supported zinc monatomic catalyst.
Example 2
Preparation method of carbon nanotube-loaded ruthenium monatomic catalyst
(1) 0.2mmol of chloroauric ruthenium is added into 100ml of ethanol for dissolution, 0.8mmol of aniline is added as a nitrogen-containing compound after complete dissolution, and finally 1g of carbon nano tube is added, and the mixture is magnetically stirred for 5 hours.
(2) The solid was recovered by centrifugation and dried overnight at 60 ℃ to give a black solid.
(3) The resulting solid was redispersed in ethanol under nitrogen, 0.2g of sodium borohydride was added as a reducing agent and stirred at 80 ℃ for 10h.
(4) The black powder was obtained by centrifugation and recovery, and drying overnight at 60 ℃.
(5) And (3) putting the dried black powder into a tubular furnace, heating to 400 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, maintaining for 2 hours, and naturally cooling to room temperature to obtain black solid powder, namely the ruthenium monatomic catalyst loaded by the carbon nano tube.
Example 3
Preparation method of graphite supported iron monatomic catalyst
(1) 0.1mmol ferric trichloride is added into 100ml acetone for dissolution, after the ferric trichloride is completely dissolved, 0.1mmol pyridine is added as a nitrogen-containing compound, and finally 5g graphite powder is added, and the mixture is magnetically stirred for 5 hours.
(2) The solid was recovered by centrifugation and dried overnight at 60 ℃ to give a black solid.
(3) And providing a nitrogen protective atmosphere, re-dispersing the obtained solid in an ethylene glycol solution, and carrying out reduction treatment by adopting microwave 600W for reaction for 20 min.
(4) The black powder was obtained by centrifugation and recovery, and drying overnight at 60 ℃.
(5) And (3) putting the dried black powder into a tubular furnace, heating to 500 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, maintaining for 2 hours, and naturally cooling to room temperature to obtain black solid powder, namely the graphite supported iron monatomic catalyst.
Property testing and results analysis
1. And (3) performing spherical aberration corrected high-angle annular dark field scanning transmission electron microscope analysis on the graphene-supported Zn monoatomic catalyst obtained in the example 1 and the carbon nanotube-supported ruthenium monoatomic catalyst obtained in the example 2.
The result is shown in fig. 1, and fig. 1 is a spherical aberration corrected high-angle annular dark field scanning transmission electron microscope image of the graphene-supported Zn monatomic catalyst obtained in example 1; fig. 2 is a transmission electron microscope image of spherical aberration corrected high-angle annular dark field scanning of the carbon nanotube-supported ruthenium monatomic catalyst obtained in example 2. From fig. 1 and 2, the white bright spots are metal catalysts, which are seen to have a monoatomic structure and to be more uniformly distributed on the support.
2. The graphene-supported Zn monoatomic catalyst obtained in example 1 and the carbon nanotube-supported ruthenium monoatomic catalyst obtained in example 2 were subjected to performance tests and results are described.
Application of graphene loaded Zn monatomic catalyst obtained in example 1 to CO2Reduction reaction, reaction conditions: coating the prepared catalyst on a glassy carbon electrode to be used as a working electrode, selecting a saturated calomel electrode as a reference electrode, selecting a Pt electrode as a counter electrode, and selecting an H-shaped electrolytic cell for CO2Electroreduction test, CO2And introducing the gas into a working electrolytic cell, and then flowing out to enter chromatographic detection. The result shows that the graphene loaded Zn single-atom catalyst shows excellent CO2The electroreduction performance realizes 95 percent of CO Faraday efficiency under the potential of-0.8V (vs. RHE), can stably run for 24h, and has high activity and stability.
The carbon nanotube-supported ruthenium monatomic catalyst obtained in example 2 is applied to selective hydrogenation of quinoline, and the reaction conditions are as follows: quinoline 0.2mmol, acetic acid 2mL as solvent, catalyst 2mg, hydrogen pressure 3MPa, reaction temperature 130 ℃, reaction time 10h. The results indicate that conversion of quinoline is > 99% and selectivity of 1,2,3, 4-tetrahydroquinoline is > 99%. After 8 times of repetition, the conversion of quinoline was maintained above 80% with a selectivity of > 99% for 1,2,3, 4-tetrahydroquinoline. Has high activity and stability.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a doped transition metal monatomic catalyst is characterized by comprising the following steps:
dissolving soluble transition metal salt solution, sp2Fully mixing the carbon material and the nitrogen-containing compound, and recovering and drying to obtain a solid compound;
dispersing the solid compound in a solvent to obtain a mixed solution;
and providing a protective atmosphere, mixing the mixed solution with a reducing agent to perform a reduction reaction, drying to obtain a monatomic catalyst precursor, and calcining the monatomic catalyst precursor to obtain the doped transition metal monatomic catalyst.
2. Method for preparing a doped transition metal monatomic catalyst according to claim 1, characterized in that said sp2The carbon material is selected from at least one of graphene and graphene derivatives; and/or the presence of a gas in the gas,
the nitrogen-containing compound is selected from nitrogen-containing compounds with conjugated structures.
3. The method of claim 2, wherein the graphene derivative is at least one selected from the group consisting of carbon nanotubes and fullerenes; and/or the presence of a gas in the gas,
the nitrogen-containing compound with a conjugated structure is selected from at least one of substituted or unsubstituted aniline, pyridine, melamine and imidazole.
4. The method for preparing a doped transition metal monatomic catalyst according to any one of claims 1 to 3, wherein the transition metal salt solution, sp2The carbon material and the nitrogen-containing compound are mixed in an amount of (0.01 to 4) mmol: 1 g: (0.01-4) mmol of the above-mentioned components.
5. The method for preparing a doped transition metal monatomic catalyst according to any one of claims 1 to 3, wherein the solvent is at least one selected from the group consisting of water, ethanol, ethyl acetate, methylene chloride, tetrahydrofuran, toluene, and pyridine.
6. The method for preparing a doped transition metal monatomic catalyst according to any one of claims 1 to 3,
the soluble transition metal salt in the soluble transition metal salt solution is selected from at least one of soluble sulfate, soluble sulfite, soluble nitrate, soluble acetate, soluble chloride, soluble bromide, soluble iodide and soluble acetylacetone of transition metal;
and the transition metal is selected from any one of Ru, Rh, Pd, Ir, Pt, Au, Fe, Co, Ni, Mn, Cu, V, Ti and Zn.
7. The method for preparing a doped transition metal monatomic catalyst according to any one of claims 1 to 3, wherein the reducing agent is at least one selected from the group consisting of citric acid, sodium borohydride, formaldehyde, ethylene glycol, hydrogen, and carbon monoxide.
8. The method for preparing a doped transition metal monatomic catalyst according to any one of claims 1 to 3,
in the drying treatment step, the drying treatment temperature is 60-120 ℃, and the drying treatment time is 2-10 hours; and/or the presence of a gas in the gas,
in the step of the reduction reaction, the temperature of the reduction reaction is 25-500 ℃, and the time of the reduction reaction is 10 minutes-10 hours; and/or the presence of a gas in the gas,
in the step of calcining, the temperature of calcining is 350-1000 ℃, and the time of calcining is 10 minutes-10 hours.
9. A doped transition metal monatomic catalyst, characterized in that the doped transition metal monatomic catalyst is prepared by the preparation method of the doped transition metal monatomic catalyst according to any one of claims 1 to 8.
10. Use of a doped transition metal monatomic catalyst prepared by the method for preparing a doped transition metal monatomic catalyst according to any one of claims 1 to 8 in a battery.
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